CN113149305A - Treatment method of glycerol wastewater - Google Patents
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Abstract
The invention relates to the technical field of glycerol wastewater recycling treatment, in particular to a glycerol wastewater treatment method, which comprises the following steps: chlorination treatment, oxidation treatment, reduced pressure evaporation treatment and tail gas treatment. The method can remove most of organic pollutants such as glycerol, organic carboxylic acid, dichloropropanol and the like in the wastewater, is suitable for the glycerol wastewater with different concentrations, and has the glycerol removal rate of over 99 percent; and meanwhile, hydrogen chloride, chlorine, trichloromethane, 1, 2-trichloroethane and other components in the reaction tail gas are transferred to a liquid phase through sodium hydroxide solution absorption and low-temperature calcium chloride solution condensation, and finally the tail gas is discharged up to the standard, so that the recycling treatment of the glycerol wastewater is realized.
Description
Technical Field
The invention relates to the technical field of wastewater recycling treatment, in particular to a treatment method of glycerol wastewater.
Background
In recent years, as the glycerol method for producing epichlorohydrin has the advantages of low raw material cost, few byproducts, mild reaction conditions and the like, attention is gradually drawn to the method, the method mainly comprises two steps, namely firstly, glycerol and hydrogen chloride gas are subjected to chlorination reaction under the action of a catalyst (generally small molecular carboxylic acids such as acetic acid, oxalic acid, succinic acid and the like) to generate dichloropropanol, and then the dichloropropanol is subjected to cyclization saponification reaction in an alkaline solution to finally obtain the epichlorohydrin.
The glycerol wastewater is from cyclization saponification reaction, and the wastewater contains a large amount of organic pollutants and salts such as glycerol, glycidol, acetic acid or oxalic acid, succinic acid, dichloropropanol and the like. At present, various processes such as adsorption, catalytic wet oxidation and extraction are tried to treat the wastewater in China, but the processes all have some problems.
Chinese patent publication No. CN 101531442A discloses a method and an apparatus for treating wastewater from epichlorohydrin production using glycerol as a raw material, in which an adsorbent is placed in different adsorption apparatuses that can be used alternately to adsorb glycerol in wastewater alternately, and finally sodium chloride-containing wastewater from which glycerol is removed is obtained as saline water for chlor-alkali industry, and elution wastewater of the adsorbent is biologically treated and discharged. The alternate adsorption-desorption process is complex, the adsorption quantity of the adsorbent is low, and the adsorbent can only be used for low-concentration glycerol wastewater.
Chinese patent publication No. CN 105645636 a discloses a method for treating wastewater from epoxy resin synthesis, in which glycerin in wastewater is oxidized and decomposed by catalytic wet oxidation reaction, and then the content of organic substances is further reduced by adsorption treatment, so as to obtain a sodium chloride solution with TOC less than 10mg/L, which can be directly used as brine in chlor-alkali industry. The method has the defects that the investment of catalytic wet oxidation equipment is huge, and the conditions of catalytic wet oxidation reaction are high temperature and high pressure, so that a great safety risk exists.
Chinese patent publication No. CN102503014A discloses a method for treating salt-containing glycerol wastewater, which comprises adding n-butanol with the amount of 1.3-3.3 times of the wastewater amount into the salt-containing glycerol wastewater to crystallize and separate out sodium chloride in the wastewater, and layering liquid phase; rectifying the upper organic phase, recovering n-butanol, and obtaining 99.9% pure glycerol as a product; filtering the lower water phase, refluxing and extracting the filtrate, and washing and recovering the crystallized sodium chloride. The method has the problems of high energy consumption of rectification, easy loss of an extracting agent, secondary pollution and the like.
The current glycerol-containing wastewater resource treatment has the following problems:
(1) most of treatment process targets are single, only the glycerol in the wastewater can be removed, and the removal effect on other organic pollutants in the wastewater is avoided;
(2) the concentration range of the glycerol treated by different processes is small, and the method is generally only suitable for the glycerol wastewater containing sodium chloride and is not suitable for the glycerol wastewater containing calcium chloride.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a method for treating glycerol wastewater, which can remove most of organic pollutants in glycerol wastewater, is suitable for glycerol wastewater with different concentrations, has a glycerol removal rate of 99% or more, and can recover inorganic salts in glycerol wastewater to realize resource treatment of glycerol wastewater.
The technical purpose of the invention is realized by the following technical scheme, and the method for treating the glycerol wastewater comprises the following steps:
s1, chlorination: heating the glycerol wastewater, introducing hydrogen chloride gas to obtain a first reaction solution, wherein the molar weight ratio of the introduced hydrogen chloride gas to the glycerol in the glycerol wastewater is 6-12: 1;
s2, oxidation treatment: adding inorganic base into the first reaction solution, adjusting the pH value of the first reaction solution, heating, and introducing chlorine gas to obtain a second reaction solution;
s3, reduced pressure evaporation treatment: introducing hydrogen chloride gas into the second reaction solution, and then performing reduced pressure evaporation to obtain inorganic salt and evaporated effluent;
and S4, tail gas treatment.
The method comprises the following steps of firstly, carrying out chlorination reaction on hydrogen chloride gas and glycerol in wastewater to generate 1, 3-dichloropropanol and 1, 2-dichloropropanol, and obtaining a first reaction liquid, wherein the reaction process comprises the following steps:
then adding inorganic alkali, adjusting the first reaction solution to be alkaline, introducing chlorine, and carrying out oxidation reaction and alpha-hydrogen substitution reaction on dichloropropanol in the solution and the chlorine to generate products such as trichloromethane, 1, 2-trichloroethane, formate and the like to obtain a second reaction solution; and continuously introducing hydrogen chloride gas into the second reaction liquid, converting formate, acetate and the like in the second reaction liquid into carboxylic acid such as formic acid, acetic acid and the like, carrying out reduced pressure evaporation treatment on the solution, evaporating the formic acid, acetic acid and water in the solution in a gas mode to obtain inorganic salt, and discharging the evaporated water after biochemical treatment to reach the standard.
Preferably, in the step S1, after the glycerin wastewater is heated to 50 to 100 ℃, hydrogen chloride gas is introduced.
Preferably, in step S2, the inorganic base is sodium hydroxide and/or calcium hydroxide.
Further preferably, in step S2, the pH of the first reaction solution is adjusted to 7 to 14, and an inorganic base is added to adjust the pH of the solution so as to appropriately neutralize carboxylic acids such as formic acid and acetic acid generated in the subsequent oxidation treatment step, thereby generating products such as formate and acetate.
Further preferably, in the step S2, the first reaction solution is heated to 40 to 90 ℃.
Preferably, in the step S2, the ratio of the molar amount of the chlorine gas to the molar amount of the glycerol in the wastewater is 2-5: 1.
Preferably, in the step S3, the ratio of the molar amount of the hydrogen chloride gas to the total molar amount of the formic acid and the acetic acid in the wastewater is 4-8: 1.
Preferably, in step S3, the evaporated water is biochemically treated and then discharged after reaching standards.
Preferably, in the step S4, the exhaust gas generated in the steps S1, S2 and S3 is sequentially passed through a sodium hydroxide solution and a calcium chloride solution, and the temperature of the calcium chloride solution is-20 to 0 ℃.
In conclusion, the invention has the following beneficial effects:
firstly, the method can remove most of organic pollutants in the wastewater, such as glycerol, organic carboxylic acid, dichloropropanol and the like, is suitable for the glycerol wastewater with different concentrations, and has the glycerol removal rate of over 99 percent.
Secondly, the pH of the first reaction solution is adjusted by using sodium hydroxide and calcium hydroxide, no new ions are introduced, and sodium ions and calcium ions can be recovered through the subsequent reduced pressure evaporation treatment step.
And thirdly, the tail gas sequentially passes through a sodium hydroxide solution and a low-temperature calcium chloride solution, so that the hydrogen chloride, chlorine, trichloromethane, 1, 2-trichloroethane and other components in the tail gas can be absorbed, the components are transferred to a liquid phase, and finally the tail gas is discharged after reaching the standard.
Fourthly, the invention can utilize the glycerol method to produce the excessive hydrogen chloride when the epichlorohydrin is used for preparing the dichloropropanol in the first step, thereby reducing the exhaust emission of the hydrogen chloride.
Drawings
FIG. 1 is a schematic diagram of the steps of the treatment method of glycerol wastewater in the first embodiment.
Detailed Description
The present invention is described in further detail below with reference to examples, which are intended to facilitate the understanding of the present invention and are not intended to limit the present invention in any way. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The glycerol wastewater taken in the following embodiments of the invention is wastewater generated in the saponification reaction process of epichlorohydrin, and the glycerol wastewater mainly contains the following components in percentage by weight: 2.1 percent of glycerin, 1.5 percent of glycidol, acetic acid, dichloropropanol and other organic matters, the content of sodium chloride is 16.3 percent, and COD in the wastewater is 48600 mg/L.
Example 1
As shown in fig. 1, S1, chlorination: heating glycerol wastewater to 100 ℃, introducing hydrogen chloride gas for reaction, wherein the molar weight of the introduced hydrogen chloride gas is 12 times of that of glycerol in the wastewater, and obtaining a first reaction solution after the reaction is finished;
s2, oxidation treatment: adding sodium hydroxide into the first reaction solution to adjust the pH value of the solution to 14, heating the solution to 90 ℃, introducing chlorine to perform oxidation reaction, wherein the molar weight of the introduced chlorine is 5 times of that of the glycerol in the first reaction solution, and obtaining a second reaction solution after the reaction is finished;
s3, reduced pressure evaporation treatment: continuously introducing hydrogen chloride gas into the second reaction liquid, wherein the molar weight of the introduced hydrogen chloride gas is 8 times of the total molar weight of formic acid and acetic acid in the second reaction liquid, introducing the hydrogen chloride gas, performing reduced pressure evaporation to obtain sodium chloride salt, selling the sodium chloride salt, and discharging the evaporated water after biochemical treatment;
s4, tail gas treatment: absorbing tail gas generated in the chlorination treatment step, the oxidation treatment step and the reduced pressure evaporation treatment step by using a sodium hydroxide solution, condensing by using a calcium chloride solution at the temperature of minus 20 ℃, and fully condensing to ensure that the tail gas reaches the standard and is discharged.
Example 2
The present embodiment is different from embodiment 1 in that: in step S1, heating the glycerol wastewater to 50 ℃, and introducing hydrogen chloride gas with the molar weight 6 times of that of glycerol in the wastewater; in step S2, adjusting the pH value of the solution to 7, heating to 40 ℃, and introducing chlorine with the molar weight 2 times of that of the glycerol in the first reaction solution; in step S3, the molar weight of the hydrogen chloride gas introduced is 4 times the total molar weight of formic acid and acetic acid in the second reaction solution; in step S4, the temperature of the calcium chloride solution is 0 ℃.
Example 3
The present embodiment is different from embodiment 1 in that: in step S1, heating the glycerol wastewater to 75 ℃, and introducing hydrogen chloride gas with the molar weight 9 times of that of glycerol in the wastewater; in step S4, adjusting the pH value of the solution to 10.5, heating to 60 ℃, and introducing chlorine with the molar weight 3.5 times of that of the glycerol in the first reaction solution; in step S3, the molar amount of hydrogen chloride gas introduced is 6 times the total molar amount of formic acid and acetic acid in the second reaction solution; in step S4, the temperature of the calcium chloride solution was-10 ℃.
Example 4
The present embodiment is different from embodiment 1 in that: in step S4, the temperature of the calcium chloride solution is 0 ℃.
Example 5
The present embodiment is different from embodiment 1 in that: in step S3, the molar amount of hydrogen chloride gas introduced is 4 times the total molar amount of formic acid and acetic acid in the second reaction solution.
Example 6
The present embodiment is different from embodiment 1 in that: in step S1, the molar amount of hydrogen chloride gas introduced is 6 times the molar amount of glycerol in the wastewater.
In conclusion, the glycerol wastewater in the invention mainly contains organic pollutants such as glycerol, glycidol, acetic acid, dichloropropanol and the like, and also contains inorganic salt components.
Step S1, heating the glycerol wastewater to 50-100 ℃, and introducing hydrogen chloride gas, wherein the molar weight ratio of the hydrogen chloride gas to the glycerol in the wastewater is 6-12:1, performing chlorination reaction on hydrogen chloride gas and glycerol in the wastewater to generate 1, 3-dichloropropanol and 1, 2-dichloropropanol, wherein the reaction process is as follows:
after the reaction is finished, a first reaction solution is obtained.
In step S2, adjusting the pH of the first reaction solution to be alkaline by using sodium hydroxide and/or calcium hydroxide, wherein the pH is 7-14; heating the first reaction liquid to 40-90 ℃, introducing chlorine gas with the molar weight 2-5 times of that of glycerol in the wastewater, carrying out oxidation reaction on the chlorine gas and dichloropropanol in the first reaction liquid under an alkaline condition to generate formic acid and acetic acid, and carrying out oxidation reaction on the formic acid and the acetic acid and OH in the solution-A neutralization reaction is carried out, part of the neutralization reaction is converted into formate and acetate, meanwhile, chlorine and dichloropropanol also carry out alpha-hydrogen substitution reaction to generate products such as trichloromethane, 1, 2-trichloroethane and the like, and after the reaction is finished, a second reaction liquid is obtainedSpecifically, volatile, low boiling trichloromethane and 1,1, 2-trichloroethane are transferred to the gas phase with excess chlorine.
In step S3, hydrogen chloride gas with a molar amount 4-8 times of the total molar amount of formic acid and acetic acid in the second reaction solution is continuously introduced into the second reaction solution to make H in the second reaction solution+The concentration is greatly increased, so that the reversible reaction processes of formate-formic acid, acetate-acetic acid and the like in the solution move to the direction of generating carboxylic acid such as formic acid, acetic acid and the like. And then, carrying out reduced pressure evaporation on the reaction solution, evaporating the formic acid, acetic acid and water in the solution in a gas form, carrying out biochemical treatment, discharging after reaching the standard, and simultaneously obtaining inorganic salts such as sodium chloride and calcium chloride.
And finally, in the step S4, tail gases such as hydrogen chloride gas, chlorine gas, trichloromethane, 1, 2-trichloroethane and the like generated in the reactions in the steps S1, S2 and S3 sequentially pass through a sodium hydroxide solution and a low-temperature calcium chloride solution, the sodium hydroxide solution absorbs the gases such as the hydrogen chloride, the chlorine gas and the like in the tail gases, the low-temperature calcium chloride solution has a condensation effect, organic matters such as the trichloromethane, the 1,1, 2-trichloroethane and the like are condensed and transferred to a liquid phase, and finally the tail gases reach the standard and are discharged.
The concentrations of the key raw materials or the reaction conditions in examples 1 to 6 of the present invention are shown in the following table,
the tail gas discharged by the process meets the execution standard of the comprehensive emission standard GB16297-1996 of atmospheric pollutants, and the detection result is as follows.
Test data of respective substances in examples
From this table, it can be seen that, except for examples 2 and 4, the treated wastewater of the present invention has a glycerin content of less than 0.58% and a glycerin removal rate of 99% or more; and chlorine (Cl) in the discharged tail gas2) The concentration is lower than 15.9mg/m3Hydrogen chloride (HCl) concentration of less than 1.5mg/m3The concentration of non-methane total hydrocarbons is less than 130mg/m3. In connection with the execution Standard of GB16297-1996, it is known that the execution Standard requires chlorine (Cl)2) The concentration must be less than 85mg/m3The concentration of hydrogen chloride (HCl) must be less than 2.3mg/m3The concentration of non-methane total hydrocarbons must be less than 150mg/m3Therefore, the embodiments 1,3, 5 and 6 of the present invention meet the execution standard of GB 16297-1996.
In examples 2 and 4, the non-methane total hydrocarbon concentration was 392mg/m3And 980mg/m3The concentration of non-methane total hydrocarbons not meeting the national regulations must not exceed 150mg/m3And thus does not comply with the execution standard of the national integrated emission standard for atmospheric pollutants GB 16297-1996.
The detection results of the inorganic salt treated and recycled by the process are as follows.
Data for detection of inorganic salts in examples
GB/T5462-one-step 2016 industrial salt requires that the first-grade industrial dry salt meets the requirements that sodium chloride (%) > is more than or equal to 98.5, water (%) > is less than or equal to 0.50, water insoluble (%) > is less than or equal to 0.10, the total content of calcium ions and magnesium ions (%) > is less than or equal to 0.40, and sulfate ions (%) -are less than or equal to 0.50.
GB/T5462 & lt- & gt & lt 5462 & gt & lt- & gt 2016 industrial salt requires that the secondary grade of industrial dry salt meets the requirements that sodium chloride (%) > is more than or equal to 97.5, water (%) > is less than or equal to 0.80, water insoluble (%) > is less than or equal to 0.20, the total content of calcium ions and magnesium ions (%) > is less than or equal to 0.60, and sulfate ions (%) > are less than or equal to 0.90; the embodiment 2 and the embodiment 6 do not meet the requirements of the second-class product, and can be sold after further purification.
In conclusion, the sodium chloride obtained in example 1, example 3, example 4 and example 5 meets the requirements of first-class or second-class products in GB/T5462-2016 industrial salt, and can be sold to the outside.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is conceivable, and the examples presented herein demonstrate the results of applicants' actual experiments. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (9)
1. A method for treating glycerol wastewater, which is characterized by comprising the following steps:
s1, chlorination: heating glycerol wastewater, and introducing hydrogen chloride gas to obtain a first reaction solution, wherein the molar weight ratio of the hydrogen chloride gas to the glycerol in the wastewater is (6-12): 1;
s2, oxidation treatment: adding inorganic base into the first reaction solution, adjusting the pH value of the first reaction solution, heating, and introducing chlorine gas to obtain a second reaction solution;
s3, reduced pressure evaporation treatment: introducing hydrogen chloride gas into the second reaction solution, and then performing reduced pressure evaporation to obtain inorganic salt and evaporated effluent;
and S4, tail gas treatment.
2. The method for treating glycerin wastewater according to claim 1, wherein in the step S1, after the glycerin wastewater is heated to 50 to 100 ℃, hydrogen chloride gas is introduced.
3. The method for treating glycerin wastewater according to claim 1, wherein in step S2, the inorganic base is sodium hydroxide and/or calcium hydroxide.
4. The method for treating glycerin wastewater according to claim 1, wherein in step S2, the pH of the first reaction solution is adjusted to 7 to 14.
5. The method for treating glycerin wastewater according to claim 1,3 or 4, wherein in the step S2, the first reaction solution is heated to 40 to 90 ℃.
6. The method for treating glycerin wastewater according to claim 1, wherein in the step S2, the ratio of the molar amount of chlorine to the molar amount of glycerin in wastewater is 2-5: 1.
7. the method for treating glycerin wastewater according to claim 1, wherein in the step S3, the ratio of the molar amount of the hydrogen chloride gas introduced to the total molar amount of formic acid and acetic acid in the wastewater is 4-8: 1.
8. the method for treating glycerin wastewater according to claim 1 or 7, wherein in step S3, the evaporated water is biochemically treated and discharged after reaching standards.
9. The method for treating glycerin wastewater according to claim 1, wherein the step S4 is to sequentially absorb the tail gas generated in the steps S1, S2 and S3 with a sodium hydroxide solution and condense the tail gas with a calcium chloride solution, and the temperature of the calcium chloride solution is-20 to 0 ℃.
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| CN110255772A (en) * | 2019-07-04 | 2019-09-20 | 浙江德强科技有限公司 | A kind of processing method of the high salt organic waste water generated in glycerol method epoxychloropropane production process |
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| CN101784479A (en) * | 2007-08-23 | 2010-07-21 | 陶氏环球技术公司 | Total organic carbon (toc) reduction in brine via chlorinolysis |
| EP2567941A1 (en) * | 2007-08-23 | 2013-03-13 | Dow Global Technologies LLC | Brine purification |
| CN110255772A (en) * | 2019-07-04 | 2019-09-20 | 浙江德强科技有限公司 | A kind of processing method of the high salt organic waste water generated in glycerol method epoxychloropropane production process |
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